Fiber



States of America for governmental purposes the solution so that it cannot be easily spun. without the payment to us of any royalty thereon. Barium hydroxide is one of the most satisfactory We hereby dedicate the invention herein'deof the metallic compounds to use because of its scribed to the free use of the People in the terrigreater solubility and because the fiber retains m tory of theUnited States to take effect on the a high proportion of its barium while in the granting of a patent to us. precipitating bath.

-Our invention pertains to fibers composed es-' The following examples are given to illustrate sentially of casein and containing a relatively some preferred methods for insuring the comhigh percentage of metallic salts. patibility of large amounts of metallic caseinates N The object of our invention is to produce comwith spinning solutions. Proportions are given positions, suitable for spinning into fibers, comin parts. prising casein and metallic caseinates in soluble EXAMPLE 1 form, and containing a high percentage of metallic compounds. Thus the strength, water-resist- Spinning solution anceand elasticity of said fibers are greatly in- Casem 24 20 creased. Other objects will become apparent in water -'L 100 the course of the following teachings. A h ly lf n ed v etabl il (or i In forming dispersions containing casein, suit- Sodium Salt) able for spinning into fibers, it is difficult to inmixture of s d um a t p sp a 25 corporate more than a com arativel small d p h sp at amount, as about 3% (based on the weight of the Barium hydroxide EBMOHH-3HZOJ 25 Casein) for instance, of strengthening and waterwater 105-48 smooth casein dispersions of high metallic con- Patented June 1 1, 1940 FIBER Stephen P. Gould and Earle 0. Whittier, wash ington, D. 0.; dedicated to the free use of the People in the territory of the United States No Drawing. Application May,28, 193,8, I

Serial No. 210,790- r 1 Claim. (Cl. 28-1) (Granted under the act of March 3,1883, as amended April 30, 1928; 370 0. G. #57) I This application is made under the act of tioned high-percentage sulfur trioxide-contalm March 3, 1883, as amended by the act of- April ing compounds and/or phosphates. Without 30, 1928, and the invention herein described and these compounds, the addition of sodium aluclaimed, if patented, may be manufactured and minate,'for instance, in increasing amounts above used by or for. the Government of the United 2%, results in a rapidly increasing viscosity of I resisting salts, such'as calcium chloride, without causing precipitation of calcium caseinate. This 30 prevents the spinning of the dispersion. If, how- The 24 parts of casein are soaked in the 100 pts. of water for 15-30 minutes, The sulfated ever, sulfated or sulfonated (preferably to a cong ifig z g fg g fi fi gg ggg 3213;? 30 sldereble degree) aliphatic or aromatic solved. The barium hydroxide is then dissolved pounds, as for example, a sulfated vegetable oil, in the remaining quantity'of water, and the solu- Incorporated with the dispersion much larger tion' stirred mechanically into the casein comamounts of metallic compounds may beblende position. Thus a smooth dispersion is obtained, 5

into the composition Without the prec1pitat1on fre f om lumps of insoluble caseinata of the corresponding caseinate. If sodium hex- The tem erature of both the s innin solution ametaphospha'te' pymphosphate or mlxture of and the pr cipitating bath was 53 C. However, these is added to the casein composition, even other temperatures varying from room t 80 larger amounts (20-30%) of the metallic com- C maybeused pounds may be mixed with the dispersion without the separation of insoluble metallic caseinates. The Sulfated ml serves as a plasticizer' If even softer fibers are desired, the amount of Inor anic bisulfit and a imonium aria 02:3 zze f ii bt i i n g the oil may be Increased or the fibers may be subjected to an after treatment with oil, glycerol,

tent. In the presence of these bisulfites, nonsimilar softening m f sulfated oils, such as oleic acid, are often com- The bath composltmn 1S: patible with the spinning solution. Y Parts If the metallic compound s is calcium hyulfuric a id 8 o xide, careful filtration is required to avoid Formaldehyde 5 P ing the spinnerette holes. comparatively- Dextrose 0 large unts of amphoteri compounds, suqh Water 7 as sodium alulninate, y be incorporated with This bath composition may, however, be varied. f outa too great increase in viscosity if the spin- The above procedure for incorporating large ning dispersion comprises the previously menamounts of metallic compounds into the spinning 2 solution results in fibers or greater strength and water resistance.

The following example illustrates the use of a sulfonated aromatic product, and of a high percentage of a calciumsalt.

EXAMPLE 2 Casein 124 Water 160.5 Sodium hydroxide solution (2N) 8 Calcium cymene sulfonate 7.5

Additional plasticizers may be added if a softer product is desired or the fibers may be after treated with oils.

age of sodium aluminate. Such solutions are ordinarily too viscous to spin, but in this case, the sulfated oil and hexametaphosphate present enable this to be done.

EXAMPLE 3 Casein 24 Water 125 Sodium hydroxide solution (2N) 8- A highly sulfated vegetable oil (or its sodium salt) 4.8 Sodium hexametaphosphate 1.5 Sodium a1uminate 3.6 Water--. 99.1

Casein may be sulfonated' directly by the action of chlorosuifonic acid whereby the insolubllity of the metallic caseinates may be increased. The chlorosuifonic acid is stirred directly into the dry casein; allowed to react for a short time, 15

minutes, for example, and water is then cautiously added. The alkali should be added promptly to minimize the efiect of the hydrochloric acid liberated by the reaction.

. EXAMPLE 4 Casein 24 Chlorosulfonic acid 2.0 Water Oleic acid 3.6 Sodium hexametaphosphate 1.5 Sodium hydroxide solution (2N) I15 Barium hydroxide [Ba(0H)2.8H2O] 4.42

Water $9.48

Example 3 illustrates the use of a high percent-- If the amount or chlorosulfonic acid is increased, the sodium hexametaphosphate may be omitted.

Example 5-ii1ustrates the use or a sulfated 7 higher alcohol in increasing the compatibilityof the metallic'compounds with the casein com- The bath composition and temperatures are the same for Examples 2-5, inclusive, as those given under Example 1.

The flexibility of these fibers may be improved by incorporation of an oil or fat with the sodium oleyl sulfate or by after treatment with oils or glycerin.

It will be understood that our invention is not limited to the above examples as proportions,

constituents, and substitutes may be varied over 1 a wide range. It is also possible at some concentrations to omit certain ingredients, such as, for

instance, the mixture of phosphates. The

amounts of metallic compounds may particularly be varied, and similar amphoteric compounds may be substituted for the sodium aluminate.

The general procedure is the same in the case of all the examples, i. e., the spinning solutions are extruded through any type of spinnerette normally used in the rayon industry into precipitating baths of the indicated compositions.

Having thus described our invention, what we claim for Letters Patent is:

As an article of manufacture, a fiber comprising casein, sulfonated casein, salts of sulfonated casein and of casein as its essential components; I

and fat acids. V

STEPHEN P..GOULD. EARLE o. 

